鉱山地質
Print ISSN : 0026-5209
深海産マンガン団塊の鉱物学的研究およびマンガン酸化物の合成
成因および地球化学に関連して
臼井 朗武内 寿久禰正路 徹也
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1978 年 28 巻 152 号 p. 405-420

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Deep sea manganese nodules from the Central Pacific Basin are mainly composed of 10Å manganite and δ-MnO 2 Two zones equivalent to the minerals are evidently distinguishable according to their optical properties. Microscopic and microprobe analyses revealed quite different chemical compositions and textnral characteristics of the two zones. These different feature of the two zones of nodules suggest the different conditions under which they were formed. Concentrations of 11 metal elements in the zones and inter-element relationships show that the 10Å manganite zone is a monomineralic oxide phase containing a large amount of manganese and minor amounts of useful metals, and that the δ-MnO 2 zone which is apparently homogeneous under the microscope is a mixture of three or more different minerals. The chemical characteristics of the two zones can explain the variation of bulk composition of deep sea manganese nodules and inter-element relationships previously reported, suggesting that the bulk compositions are attributable to the mixing of the 10Å manganite and δ-MnO 2 zones in various ratios. Characteristic morphology and surface structure of some types of nodules and their relationships to chemistry are also attribut able to the textural and chemical features of the above mentioned two phases.
Synthesis of hydrated manganese oxides was carried out in terms of the formation of manganese minerals in the ocean. The primary product which is an equivalent to δ-MnO 2 was precipitated from Mn 2+ -bearing alkaline solution under oxigenated condition by air bubbling at one atmospheric pressure and room temperature. The primary product was converted to a l0Å manganite equivalent by contact with Ni 2+, Cu 2++ or CO2+ chloride solutions. This reaction caused the decrease of Ni 2+, Cu 2+ or CO2+ concentrations and the increase of Na + concentration in the solution. The reaction also proceeded even in diluted solutions of nickel chloride and resulted in a complete removal of Ni 2+ from the solution. Reaction products were exclusively 10Å manganite equivalents and their chemical compositions were very similar to those of 10Å manganite in manganese nodules. The maximum value of(Cu+Ni+Co)/Mn ratio of 10Å manganite zones in manganese nodules is 0.16, and the Ni/Mn ratio of synthetic 10Å manganite ranges from 0.15 to 0.18 with the average of 0.167.

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